NO dissociation pathways on Rh(1 0 0), (1 1 0), and (1 1 1) surfaces: A comparative density functional theory study

The chemisorption and dissociation pathways of NO on the Rh(1 0 0), (1 1 0), and (1 1 1) surfaces are studied by the plane-wave density functional theory (DFT) with CASTEP program. In addition, the electronic and geometrical effects that affect the NO dissociation reactions have been investigated in detail. The calculation results are presented as following: The effective activation energies of the best NO dissociation pathways on the Rh(1 0 0), the Rh(1 1 0), and the Rh(1 1 1) are 0.63, 0.66 and 1.77 eV, respectively. The activity of the Rh planes for NO dissociation is in the order of Rh(1 0 0) ≈ Rh(1 1 0) > Rh(1 1 1). The low dissociation barrier for Rh(1 0 0) and Rh(1 1 0) is associated with the existence of a lying-down NO structure which acts as a precursor for dissociation. By Mulliken population analysis and structure analysis, both electronic and geometrical effects are found to affect the NO dissociation reactions, but the geometrical effect exceed the electronic. The energy decomposition scheme has been used to provide further insight into the NO dissociation reactions. Based on the calculations, the interaction energy between N and O in the transition state on the Rh(1 1 1) is found much larger than that on the Rh(1 0 0) and the Rh(1 1 0). The major differences of should originate from the variation of the bonding competition effect.     

Band parameters of α-LiBeN semiconductor from density functional calculations

The structural, elastic, electronic, optical and thermal properties of α phase in LiBeN semiconductor have been studied using pseudo-potential plane wave method based on the density functional theory. The computed lattice parameter agrees well with previous theoretical work. The elastic constants and their pressure dependence are predicted using the static finite strain technique. A set of isotropic elastic parameters and related properties, namely bulk and shear moduli, Young’s modulus, Poisson’s ratio, average sound velocity and Debye temperature are numerically estimated in the frame work of the Voigt–Reuss–Hill approximation for α-LiBeN polycrystalline aggregate. The assignments of the structures in the optical spectra and band structure transitions have been examined and discussed. The thermal effect on heat capacities is investigated by the quasi-harmonic Debye model. To the best of our knowledge, most of the studied properties of the material of interest are reported for the first time.     

CO adsorption on oxygen-modified molybdenum surfaces

Structures of carbon monoxide layers on the oxygen-modified Mo(1 1 0) and Mo(1 1 2) surfaces have been investigated by means of density-functional (DFT) calculations. It is found that CO molecules adsorb at hollow sites on the O/Mo(1 1 0) surface and nearly atop Mo atoms on the O/Mo(1 1 2) surface. The favorable positions for adsorption are shown to be near protrusions of electron density above the Mo surface atoms. The presence of oxygen on the molybdenum surface significantly reduces the binding energy of the CO molecule with the substrate; on the oxygen-saturated Mo(1 1 0) surface, the adsorption of CO is completely blocked. The calculated local densities of states (LDOS) demonstrate that the O 2s peak for O adsorbed on Mo(1 1 0) surface is at −19 eV (with respect to the Fermi level), while for the oxygen atom of an adsorbed CO molecule the related 3σ molecular orbital gives rise to a peak at −23 eV. This difference stems from the bonding of the O atom either with Mo surface for adsorbed O or with C atom in adsorbed CO, and therefore the position of the O 2s peak in photoemission spectra can serve as a convincing argument in favor of either the presence or absence of the CO dissociation on Mo surfaces.     

Evolution of spectroscopic information over the last decade and its effect on line-by-line calculations for validation of radiation codes for climate models

Five HITRAN's editions (since 1992) and three radically new H₂O spectral databases have been tested for their usefulness in line-by-line benchmark calculations for radiation code validations. The longwave calculations for the mid-latitude summer (MLS) atmosphere with the different HITRAN's editions revealed a good convergence (maximal discrepancies since decreased to in our flux calculations with 1992-2002 and 1996-2002 HITRAN's editions, respectively). The shortwave calculations with different HITRAN's editions revealed a good agreement: discrepancies in downward fluxes absorbed by the MLS atmosphere are less than , i.e. 0.5% for the all HITRAN's editions since 1992. It has been determined that it is unreasonable to replace HITRAN by any new H₂O spectral database in benchmark calculations, although they contain essentially more spectral lines than HITRAN (up to ∼10 times). Moreover, it has been found that no new database could be useful for explaining the “anomalous absorption” problem. Two latest water vapor continuum models have been tested as well. It has been found out that these models are the main source of uncertainties in the present and previous calculations: discrepancies for the MLS atmosphere reached ∼3 and in the longwave and shortwave flux calculations, respectively.     

Frequency combinations in the magnetoresistance oscillations spectrum of a linear chain of coupled orbits with a high scattering rate

The oscillatory magnetoresistance spectrum of the organic metal (BEDO)₅Ni(CN)₄. 3C₂H₄(OH)₂ has been studied up to 50 T, in the temperature range from 1.5 K to 4.2 K. In high magnetic field, its Fermi surface corresponds to a linear chain of quasi-two-dimensional orbits coupled by magnetic breakdown (MB). The scattering rate consistently deduced from the data relevant to the basic α and the MB-induced β orbits is very large which points to a significant reduction of the chemical potential oscillation. Despite of this feature, the oscillations spectrum exhibits many frequency combinations. Their effective masses and (or) Dingle temperature are not in agreement with either the predictions of the quantum interference model or the semiclassical model of Falicov and Stachowiak.     

The AΠu state of : Electric properties, fine and hyperfine coupling constants, and magnetic moments (g-factors). A theoretical study

Several properties are calculated for A²Π_u of —the majority for the first time—including electric and magnetic moments, and fine/hyperfine structure (fs/hfs) parameters. The new results are compared with our previous ones for X² and B² of [P.J. Bruna, F. Grein, J. Mol. Spectrosc. 227 (2004) 67–80]. The electric quadrupole Θ and hexadecapole Φ moments, polarizability α, and hfs constants a, b, c, d, eQq₀, eQq₂ are evaluated at the density functional theory (DFT) level [B3LYP/aug-cc-pVQZ]. The fs constants (spin–orbit coupling A_Π, Λ-doubling p, q, spin-rotation γ_Π), and magnetic moments (g-factors) are obtained via 2nd-order sum-over-states expansions, using wavefunctions and matrix elements obtained with a multireference configuration interaction (MRDCI) method, and the Breit–Pauli Hamiltonian. At equilibrium, 2nd-order properties of A²Π_u are dominated by its coupling with B². For the A state, two independent components are reported for traceless tensor properties (multipoles Θ and Φ; hfs parameters c/d and q₀/q₂) and three for traced properties (polarizability α and g-factors), i.e., one more component than for axially symmetric Σ states. The currently available experimental data on — limited to A_Π, p, and q—are well reproduced by our theoretical results.     

Diffusion of oxygen atom in the topmost layer of the Si(1 0 0) surface: Structures and oxidation kinetics

The incorporations and migrations of the atomic oxygen in the topmost layer Si(1 0 0)-p(2 × 2) silicon surface, are investigated theoretically using density functional theory. We show that the diffusion is dependent on the starting and the final surrounding environment and does not simply consist in hops from one silicon-silicon bond to another. The activation energies range from 0.11 eV to 2.59 eV.     

A theoretical study of CH4 dissociation on Pt(1 0 0) surface

Density functional theory calculations have been performed on the adsorption of H and CH₃, and the dissociation of CH₄ on Pt(1 0 0) surface. It was found that H was adsorbed on the top and bridge sites, while CH₃ was adsorbed only on the top site. The coadsorption of methyl and hydrogen which has also been investigated shows that the interaction between the two adsorbates is stabilising. In addition, two distinct pathways were explored, differing by the initial adsorbed state of CH₄. They converge readily to the same transition state corresponding to an activation energy value of 0.53 eV. These results compare favourably with existing data in the literature for Pt(1 1 1) and Pt(1 1 0).